Process for polymerizing olefin oxides with a catalyst consisting of a zinc alkyl and an oxide or hydroxide of a group iia metal



United States Patent 3,230,207 PROCESS FOR POLYMERIZING OLEFIN OXIDFfiWITH A CATALYST CONSISTING OF A ZENC ALKYL AND AN OXIDE 0R HYDROXIDE OFA GROUP IIA METAL Hiroshi Daimon, Kosaku Kamio, and Shimpei Kojima,Toyarna-ken, Japan, assignors to Nippon Carbide Kogyo Kabushiki Kaisha,Chiyoda-ku, Tokyo, Japan, a corporation of Japan N0 Drawing. Originalappiication Mar. 1, 1961, Ser. No. 92,458. Divided and this applicationSept. 28, 1962, Ser. No. 227,086

Claims priority, application Japan, Mar. 5, 1960, 35/7,344 4 Claims.(Cl. 26088.3)

This application is a division of our copending application No. 92,458.

This invention relates to the preparation of homopolymers and copolymersof olefin oxides. More particularly, this invention relates to thepreparation of these polymers by homopolymerizing or copolymerizingolefin oxides in the presence of a catalyst system consisting of anorganozinc compound and a specific cocatalyst.

The term polymers as used in this application means homopolymers andcopolymers: the term to polymerize means to homopolymerize and tocopolymerize; the term olefin oxides means compounds having at least oneepoxy group in the molecule.

Olefin oxides have previously been polymerized in the presence of anorganozinc compound which acts as a catalyst. However, when thepolymerization of olefin oxides is efiectecl with only an organozinccompound being used as the catalyst, the yield of polymers is very low.Additionally, the polymers produced by this polymerization have a lowmolecular weight and low crystallinity. Further, when the olefin oxidesto be polymerized are olefin oxides containing not less than threecarbon atoms in the molecule, polymerization in the presence of anorganozinc compound gives very poor results.

It is an object of this invention to provide for polymerizing olefinoxides into high molecular weight polymers with excellent yields.

It is a further object of the invention to produce olefin oxide polymershaving a degree of crystallization suitable for desired applications.

It is a further object of the invention to produce olefin oxide polymershaving high crystallinity which was difficult to obtain heretofore.

It is still a further object of the invention to produce stable olefinoxide polymers.

It is yet a further object of the invention to produce olefin oxidepolymers having olefinic double bonds and having no cross linkage in themolecule.

Other objects of this invention will become apparent from the followingdetailed description.

The olefin oxides which can be homopolymerized or copolymerizedaccording to this invention include ethylene oxide, propylene oxide,butene oxide, isobutene oxide, epichlorohydrin, epibromohydrin,trifiuoromethyl ethylene oxide, cyclohexene oxide, phenylglycidyl ether,butadiene oxide, butadiene dioxide and styrene oxide.

We have found that a catalyst system consisting of at least one materialselected from the following class (A) and at least one material selectedfrom the following class (B) is efiective for the polymerization ofolefin oxides:

(A) Dialkyl zinc having the general formula 3,230,207 Patented Jan. 18,1966 wherein R and R represent hydrocarbon radicals having not more than4 carbon atoms.

(B) Metal oxides and metal hydroxides of metals belonging to the Ilagroup in the Periodic Table.

The compounds of the class (A) include dimethylzinc, diethylzinc anddibutylzinc.

The metal oxides include magnesium oxide, calcium oxide, strontium oxideand barium oxide.

The metal hydroxides include calcium hydroxide, strontium hydroxide andbarium hydroxide.

The mechanism by which the compounds belonging to the class (B)remarkably increase the catal tic activity of organozinc compoundsbelonging to the class (A) has not yet been clarified. However, in viewof the results of an enormous number of polymerization experiments, itis believed that the polymerization activity of said organozinccompounds is enhanced by a change of electron state caused bycoordination of atoms having large electronegativity value in thecompounds belonging to the class (B).

The effect of use of both compounds belonging to class (A) and class (B)together as compared with the effect of the use of each of themseparately appears from the following:

Polymerization of propylene oxide in a closed tub at C. for 18 hours inthe presence of diethylzinc of class (A) as the sole catalyst gives onlya liquid low mo lecular weight polymer. High polymers are not obtainedunder the same conditions in the presence of a compound belonging toclass (B) used as the sole catalyst. On the contrary, the polymerizationof propylene oxide at 80 C. for 18 hours in the presence of a catalystsystem consisting of compounds belonging to both classes (A) and (B)gives a high polymer of propylene oxide with a good yield. The molecularWeight of polymers thus obtained amounts to several millions and thepolymers are of high crystallinity.

Further, properties can be improved by forming secondary crosslinkagesbetween olefin oxide polymer molecules to produce very useful syntheticresins or synthetic rubbers.

The-re are various methods to form crosslinkages between olefin oxidepolymer molecules. According to one of those methods, an olefin oxidehaving an olefinic unsaturated bond is homopolymerized or copolymerizedto introduce the olefinic unsaturated bond into the polymer and thecrosslinking reaction is effected on molding. Sometimes the unsaturatedbond of the olefin oxide having the olefinic unsaturated bond reactsduring the polymerization to give a cross linked olefin oxide polymer.

In the method of this invention compounds belonging to classes (A) and(B) react with each other in an optional method and form activecatalysts. They can, however, be used merely by simply mixing both ofthem together. A compound belonging to the class (B) can, for example,be dispersed in a suitable inert organic solvent such as, for example,ether, hexane, toluene, etc., and an organozinc compound is addedthereto. Immediately after the reaction, the mixture can be used. Also,the mixture may be allowed to stand at room temperature for an extendedperiod of time in order to allow the completion of the reaction or themixture can be subjected to a heat treatment and then used.

The ratio of the compound of the class (A) to the compound of the class(B) can be 1 part:0.00l-10,000 parts and is preferably 1 part:0.0l-10parts; it need not be an integer ratio stoichiometrically.

-In the polymerization of this invention, the amount of polymerizationcatalyst is not particularly limited, but in general the amount of theorganozinc compound to the monomer ranges from 0.001 mol percent to 10mol percent and preferably from 1 mol percent to mol percent.

The polymerization method of this invention can be carried out with awide range of temperatures, particularly from 20 C. to 300 C. andpreferably from 0 C. to 200 C.

In the method of this invention, it is preferable to use a diluent,because it facilitates the polymerization operation. As the diluent,inert solvents are generally used for the monomer. Among the usableinert solvents are: ethers such as diethyl ether, diisopropyl ether andthe like, aromatic hydrocarbons such as benzene, toluene and the like,aliphatic or cycloaliphatic hydrocarbons such as n-hexane, n-heptane,cyclohexane, petroleum ether, petroleum benzene and the like, andhalogenated hydrocarbons such as chloroabenzene, methylene chloride,chloroform, carbon tetrachloride and the like. Also, these can be usedas mixtures.

i In the following examples all parts and percents are based on weightunless otherwise specified.

Example 1 Air in a stainless steel vessel of 100 ml. volume was replacedwith nitrogen. Magnesium oxide (2 mol percent to propylene oxide)pulverized in parts of nhexane and n-hexane solution containing 0.3 partof diethylzinc were added to the stainless steel vessel. After severalminutes, 10 parts of propylene oxide were added and the vessel wasclosed and placed under thermostat control at 80 C. After 18 hours thevessel was cooled, and the resulting polymer product was taken out anddried under vacuum. 10.5 parts of white crude polymer product wasobtained.

Examples 24 In these examples, the following compounds were used as thecocatalysts in place of magnesium oxide in Example 1. The amount ofcocatalyst of 2 mol percent to propylene oxide used. The value ofpolymer yield is calculated from the amount of dried polymer productless the amount of catalyst'contained thereim Cocatalyst Polymer yield(percent) 1 Calcium hydroxide Strontium oxidem. Barium oxide What isclaimed is:

1. A method for the preparation of polymers of olefin oxides comprisingpolymerizing an olefin oxide having less than 10 carbon atoms andconsisting of atoms selected from the group consisting of H, C, O andhalogens at 0 to 200 C., in the presence of a catalyst system consistingof 0001-10 mol percent based on the monomer, of a material of a class(A) of dialkyl zinc having the general formula of RZnR wherein R and Rare hydrocarbon radicals having not more than 4carbon atoms and0.00110,000 parts by weight based on the material of class (A), of amaterial of a class (B) selected from the group consisting of metaloxides and metal hydroxides of the metals belonging to the Ila group inthe Periodic Table.

2. A method according to claim 1 wherein the olefin oxide is ethyleneoxide.

3. A method according to claim 1 wherein the olefin oxide is propyleneoxide.

4. A method according to claim 1 wherein the olefin oxide is butadienemonoxide which is polymerized into a solid polymer.

References Cited by the Examiner UNITED STATES PATENTS 1/1950 Stewart2602 4/196'2 Bailey 26088.3

OTHER REFERENCES JOSEPH L. SCHOFER, Primary Examiner. WILLIAM H. SHORT,Examiner.

W. G. GOODSON, W. HOOVER, Assistant Examiners.

1. A METHOD FOR THE PREPARATION OF PLYMERS OF OLEFIN OXIDES COMPRISING POLYMERIZING AN OLEFIN OXIDE HAVING LESS THAN 10 CARBONS ATOMS AND CONSISTING OF ATOMS SELECTED FROM THE GROUP CONSISTING OF H, C, O AND HALOGENS AT 0 TO 200*C., IN THE PRESENCE OF A CATALYST SYSTEM CONSISTING OF 0.001-10 MOL PERCENT BASED ON THE MONOMER, OF A MATERIAL OF A CLASS (A) OF DIALKYL ZINC HAVING THE GENERAL FORMULA OF R-ZN-R'' WHEREIN R AND R'' ARE HYDROCARBON RADICALS HAVING NOT MORE THAN 4 CARBON ATOMS AND 0.001-10,000 PARTS BY WEIGHT BASED ON THE MATERIAL OF CLASS (A), OF A MATERIAL OF A CLASS (B)SELECTED FROM THE GROUP CONSISTING OF METAL OXIDES AND METAL HYDROXIDES OF THE METALS BELONGING TO THE IIA GROUP IN THE PERIODIC TABLE. 